Formation of glycol bisphosphate compounds

ABSTRACT

Glycol bisphosphate compounds are formed by first hydrolytically condensing a dihydrocarbylhalophosphate to form a tetrahyrocarbyl pyrophosphate and then reacting the pyrophosphate with a cyclic ether to form the glycol bisphosphate.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is a novel process for forming glycol bisphosphatecompounds.

2. Description of the Prior Art

Glycol bisphosphate compounds are a known class of organophosphoruscompounds which are useful, for example, as flame retardants inpolymers. These compounds have the general formula ##STR1## where R ishydrocarbyl (e.g., alkyl, aryl, alkaryl, arylalkyl, etc.) and R' ishydrocarbylene (e.g., alkylene, arylene, etc ). For example, R can bephenyl with R' being alkylene, such as ethylene, isopropylene,neopentyl, etc.

This class of compounds may be prepared by reacting adihydrocarbylhalophosphate (e.g., diphenylchlorophosphate) with a glycolin the presence of an amine as described in Biorg. Khim., 11(6) 845-848(1985). However, such a route needs to be run at relatively lowtemperatures (0°-10° C.) in order to achieve good yields. If thisreaction is run at room temperature, it has been found that the majorproduct is triphenylphosphate. This reaction also use equimolar amountsof amine which produces an amine salt which must be filtered from thereaction mixture. Also, a solvent is needed in such a process.

Another approach to making glycol bisphosphate compounds is described inJapanese Patent Publication No. 74 40342 which shows reaction ofphosphorus oxytrichloride with a glycol followed by reaction withphenol.

U.S. Pat. No. 3,492,373 teaches condensation of a bisphenol or bisphenolalkane with a monophenol, a phenylphosphorous halide, or a mixture ofphenylphosphorous halide and monophenol.

M. Combey et al in U.S. Pat. No. 3,869,526 speak of formation ofbis(phosphates) by one of two methods. The first involves reaction of analcohol, phenol or both with phosphorus oxychloride and a diol in thatorder. The second involves transesterification of a triorganophosphatewith a diol, polyol or diphenol preferably in the presence of a metallictransesterification catalyst.

SUMMARY OF THE INVENTION

The instant process, in one embodiment, is a two step procedure forforming glycol bisphosphates. The first step involves the hydrolyticcondensation of a dihydrocarbylhalophosphate to form a tetrahydrocarbylpyrophosphate. The second step involves reaction of the pyrophosphatewith a cyclic ether to form the desired glycol bisphosphate.

Another embodiment of the invention is the reaction of the pyrophosphatewith cyclic ether to form the bisphosphate.

Additionally, it is deemed that the first step of preparing thepyrophosphate compound by hydrolytic condensation of adiarylhalophosphate is novel and another aspect of the instantinvention.

DETAILED DESCRIPTION OF THE INVENTION

The hydrolytic condensation of the dihydrocarbylhalophosphate involvesreaction of water with a compound of the formula ##STR2## where R ishydrocarbyl (independently alkyl, aryl, alkaryl, arylalkyl, etc.) and Xis halogen. The foregoing hydrocarbyl moieties can either beunsubstituted or can be substituted with non-interfering substituents tothe instant reaction (e.g., halogen). This can be practiced attemperatures of from about 50° C. to about 170° C. and results information of a pyrophosphate compound of the formula ##STR3## where Rhas the meaning given above. R can be substituted or unsubstitutedphenyl, if desired. Examples of substituted phenyl groups R in theforegoing formula include xylyl, 2,6-dichlorophenyl, 4-tert-butylphenyl,2,3,4,5,6-pentachlorophenyl, 4-(1,3-dimethylbutyl)phenyl,3-methylphenyl, 4-chlorophenyl, 3-nitrophenyl, 4-nitrophenyl, and thelike. The hydrolytic condensation of dialkylhalophosphates is known (seeJ. Amer. Chem. Soc. Vol. 70, 3882-3886 and Vol. 71, 2268).

In order to achieve the insertion of the desired hydrocarbyl bridginggroup between the two phosphate moieties in the pyrophosphate, thatcompound is then reacted with a cyclic ether. The cyclic ether can be ofthe formula ##STR4## where each of R₁ -R₄ are independently hydrogen orsubstituted or unsubstituted alkyl or aryl, R is substituted orunsubstituted alkylene, and n is an integer of from 0 to 1.Representative ethers which can be used include ethylene oxide,propylene oxide, epichlorohydrin, epibromohydrin, cyclohexene oxide,epoxidized soybean oil, oxetane, 3,3-dimethyloxetane,3,3-bis(chloromethyl)oxetane, 3,3-bis(bromomethyl)oxetane, thediglycidyl ether of bisphenol A, the brominated diglycidyl ether orbisphenol A, and the like. The reaction of the pyrophosphate with thecyclic ether can be conducted at temperatures of from about 30° C. toabout 160° C. using molar ratios of pyrophosphate to ether ranging fromabout 1:1 to about 1:2. Advantageously, a catalytically effective amount(e.g., from about 0.1% to about 2%, by weight, based on the weight ofthe pyrophosphate) of amine or Lewis acid catalyst is used to acceleratethe reaction.

The following Examples further illustrate the instant invention.

EXAMPLE 1

This Example illustrates the preparation of tetraphenyl pyrophosphate.

To 10 moles of diphenylchlorophosphate (2686 gm) heated to 70° C. undernitrogen, was added 5 moles (90 gm) of water over a period of fivehours. The temperature was kept at 75° C. throughout the addition. Atthe end of the addition period, the reaction mixture was kept at 75°-80°C. for one hour, and the temperature was then raised and maintained at120° C. for three hours. It was then raised to 140° C. and maintained atthat temperature for an additional three hours. A reddish orange oil(2430 gm, 98.7% yield) was obtained and assayed at 96% purity by ³¹ Pnmr.

EXAMPLE 2

Ethylene glycol bis (diphenyl phosphate) was made by the followingprocedure. To the tetraphenyl pyrophosphate from Example 1 (0.5 mole,243 gm) was added 2 ml of pyridine. This mixture was heated to 70° C.under nitrogen. Ethylene oxide (43 gm, 0.98 mole) was slowly fed intothe resulting mixture at 70° C. over ten hours. At the end of this time,the excess ethylene oxide was removed by applying slight vacuum. Thereaction mixture was washed at 60° C. with 200 ml of 2% sulfuric acid,followed by 200 ml of 2% sodium hydroxide and two aliquots of 200 ml ofwater. Traces of water were removed at 100° C. under vacuum. The viscousyellow oil that remained (224.6 gm, 87.4% yield) was analyzed. Onstanding, the oil solidified (mp =38°-40° C.). The hydrogen and ³¹ P nmranalysis was consistent with the proposed structure. The materialassayed at 97.2% by high pressure liquid chromatography.

EXAMPLE 3

This Example illustrates the preparation of propylene glycol bis(diphenyl phosphate). To the tetraphenyl pyrophosphate from Example 1(0.5 mole, 243 gm), that had been heated to 70° C. under nitrogen, wasadded a solution of 32 gm (0.55 mole) of propylene oxide and 3 ml ofpyridine over a period of three hours. The reaction mixture was kept at70° C. for six hours. Excess propylene oxide was distilled from thereaction mixture. After washing and drying, as described in Example 2,there was left 218 gm of a colorless oil (80% yield). The anticipatedidentity of the product was confirmed by ¹ H and ³¹ P nmr and thematerial assayed at 96.7% purity by ³¹ P nmr.

EXAMPLE 4

Neopentyl glycol bis (diphenyl phosphate), as claimed in U.S. Ser. No.07/374,716, entitled "Novel Aromatic Bisphosphates" was made by thisExample. To tetraphenyl pyrophosphate from Example 1 (0.5 mole, 243 gm),heated to 80° C. under nitrogen, was added a solution of 3,3-dimethyloxetane (0.5 mole, 43.1 gm) and 2 ml of pyridine. The temperature wasraised to 120° C. and was kept at constant temperature for ten hours.After washing and drying as described in Example 2, there was obtained253.5 gm of a light yellow oil (89% yield). The identify of the productwas confirmed by ¹ H and ³¹ P nmr, and this material assayed at 92%purity by ³¹ P nmr.

EXAMPLE 5

Dichloroneopentyl glycol bis (diphenyl phosphate), as also claimed inU.S. Ser. No. 07/371,716, was made in this Example. It was made asdescribed in Example 4 from 0.32 mole, 154.2 gm of tetraphenylpyrophosphate, 0.32 mole (50 gm) of 3,3-bis(chloromethyl) oxetane and 2ml of pyridine. A viscous light brown oil (152.4 gm) was obtained at 75%yield. The identity of the product was confirmed by ¹ H nmr.

EXAMPLE 6

Propylene glycol bis(diphenylphosphate) was made in this Example. To 0.5mole of tetraphenylpyrophosphate (243 grams) was added 0.2 grams ofmagnesium chloride. The mixture was heated to 80° C. Propylene oxide (50ml) was slowly added over six hours with the temperature being kept at80° C. After the addition was completed, the reaction mixture was heatedto 85° C. for an additional four hours. It was then washed at 50° C.with 200 ml of 2% sulfuric acid, 200 ml of 2% sodium hydroxide, and two200 ml portions of water. After removal of traces of water at vacuum at90° C., there was left 218 grams (80.7% yield) of a colorless oil which,by ³¹ P nmr analysis, was shown to contain 84% of the desiredbisphosphate and 14% of triphenylphosphate by-product.

EXAMPLE 7

Example 6 was repeated using stannous octoate as a catalyst (at 0.3% byweight of tetraphenylpyrophosphate) and ethylene oxide in place ofpropylene oxide in order to produce ethylene glycolbis(diphenylphosphate). The results were comparable to those achieved inExample 6.

The foregoing Examples have been presented to illustrate certainembodiments of the instant invention and, for this reason, should not beconstrued in a limiting sense. The scope of protection that is sought isset forth in the claims which follow.

We claim:
 1. A process for the formation of a glycol bisphosphate whichcomprises:(a) hydrolytic condensation of a dihydrocarbylhalophosphate toform a tetrahydrocarbyl pyrophosphate, and (b) reaction of thetetrahydrocarbyl pyrophosphate with a cyclic ether to form the glycolbisphosphate.
 2. A process as claimed in claim 1 wherein thedihydrocarbylhalophosphate is a diarylhalophosphate of the formula##STR5## where Ar is an aryl moiety and X is halo.
 3. A process asclaimed in claim 1 wherein the cyclic ether is of the formula ##STR6##where each of R₁ -R₄ are independently hydrogen or substituted orunsubstituted alkyl, R is substituted or unsubstituted alkylene, and nis an integer of from 0 to
 1. 4. A process for the formation of a glycolbisphosphate which comprises:(a) hydrolytic condensation of adihydrocarbylhalophosphate of the formula ##STR7## where Ar is an arylmoiety and X is halo to form a tetrahydrocarbyl pyrophosphate, and (b)reaction of the tetrahydrocarbyl pyrophosphate with a cyclic ether toform the glycol bisphosphatewherein the condensation is conducted at atemperature of from about 50° C. to about 170° C.
 5. A process for theformation of a glycol bisphosphate which comprises:(a) hydrolyticcondensation of a dihydrocarbylhalophosphate to form a tetrahydrocarbylpyrophosphate, and (b) reaction of the tetrahydrocarbyl pyrophosphatewith a cyclic ether of the formula ##STR8## where each of R₁ -R₄ areindependently hydrogen or substituted or unsubstituted alkyl, R issubstituted or unsubstituted alkylene, and n is an integer of from 0 to1 to form the glycol bisphosphatewherein the cyclic ether is reacted ata temperature of from about 30° C. to about 160° C.
 6. A process for theformation of a glycol bisphosphate which comprises:(a) hydrolyticcondensation of a dihydrocarbylhalophosphate to form a tetrahydrocarbylpyrophosphate, and (b) reaction of the tetrahydrocarbyl pyrophosphatewith a cyclic ether to form the glycol bisphosphatewherein thecondensation reaction (a) is conducted at a temperature of from about50° C. to about 170° C. and the reaction (b) of the cyclic ether isconducted at a temperature of from about 30° C. to about 160° C.
 7. Aprocess as claimed in claim 6 wherein the reaction (b) is effected inthe presence of a catalytically effective amount of amine or Lewis acidcatalyst.
 8. A process for the formation of a glycol bisphosphate whichcomprises the reaction of a tetrahydropyrophosphate with a cyclic ether.9. A process as claimed in claim 8 wherein the tetrahydropyrophosphateis of the formula ##STR9## where R is hydrocarbyl.
 10. A process asclaimed in claim 9 wherein the tetrahydropyrophosphate is reacted with acyclic ether of the formula ##STR10## where each of R₁ -R₄ areindependently hydrogen or substituted or unsubstituted alkyl or aryl, Ris substituted or unsubstituted alkylene, and n is an integer of fromabout 0 to about 1 and the reaction is carried out at a temperature offrom about 30° C. to about 160° C.
 11. A process for the formation of aglycol bisphosphate which comprises the reaction of atetrahydropyrophosphate with a cyclic ether wherein the reaction isconducted at a temperature of from about 30° C. to about 160° C. using amolar ratio of pyrophosphate to ether ranging from about 1:1 to about1:2.
 12. A process for the formation of a glycol bisphosphate whichcomprises the reaction of a tetrahydropyrophosphate with a cyclic etherwhich comprises use of a catalytically effective amount of an amine orLewis acid catalyst.